Uv absorber compositions comprising a hydroxyphenyltriazine compound

ABSTRACT

UV absorber compositions are described, comprising (a) from 1 to 99% by weight of a hydroxyphenyltriazine compound of formula (I) wherein R 1 , R 2  and R 3  are each independently of the others C 1 -C 18  alkyl; C 2 -C 10 ,alkenyl; or phenyl-C 1 -C 4  alkyl; R 4  is hydrogen; or C 1 -C 5 alkyl; and (b) from 99 to 1% by weight of a further UV absorber selected from the group of (b) hydroxyphenyltriazines that are different from component (a), (b 2 ) benzotriazoles, (b 3 ) dibenzoylmethane derivatives and (b 4 ) camphor derivatives. The compositions are suitable as UV filters in cosmetic compositions.

The present invention relates to UV absorber compositions, to the use ofsuch compositions in protecting human and animal skin and hair from theharmful effects of UV radiation, and to their use in cosmetic andpharmaceutical formulations.

It is known that certain organic UV filters, such as, for example,poorly soluble triazine compounds, have pronounced UV filter properties.However, the solubility of such organic UV filters in solvents that aresuitable for cosmetic formulations is often inadequate.

There is strong interest in organic light-protective filters that can bereadily incorporated in cosmetic formulations, that is to say that havegood oil-solubility.

The problem of the present invention is therefore to find organic UVfilters or UV filter mixtures that have good solubility in solvents thatare suitable for cosmetic formulations.

It has now been found, surprisingly, that UV absorber compositionscomprising selected triazine compounds have such properties.

The present invention accordingly relates to a UV absorber compositioncomprising

-   -   (a) from 1 to 99% by weight of a hydroxyphenyltriazine compound        of formula    -    wherein    -   R₁, R₂ and R₃ are each independently of the others C₁-C₁₈alkyl;        C₂-C₁₀alkenyl; or phenyl-C₁-C₄alkyl;    -   R₄ is hydrogen; or C₁-C₅alkyl; and    -   (b) from 99 to 1% by weight of a further UV absorber selected        from the group of (b₁) hydroxyphenyltriazines that are different        from component (a), (b₂) benzotriazoles, (b₃) dibenzoylmethane        derivatives and (b₄) camphor derivatives.        C₁-C₁₈Alkyl radicals are straight-chain or branched alkyl        radicals such as, for example, methyl, ethyl, n-propyl,        isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or        tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl,        dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or        octadecyl.

C₂-C₁₀Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl,3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl,n-oct-2-enyl, n-dodec-2-enyl or isododecenyl.

Phenyl-C₁-C₁₀alkyl is, for example, phenylbutyl, phenylpropyl,phenylethyl or, preferably, benzyl.

The composition preferably comprises

-   -   from 5 to 95% of component (a) and    -   from 95 to 5% of component (b).

In formula (1), R₁, R₂ and R₃ preferably are each independently of theothers C₅-C₁₂alkyl.

R₁, R₂ and R₃ preferably have the same meaning.

Very special preference is given to a UV absorber composition whereincomponent (a) corresponds to formula

Preference is further given to compounds of formula (I) wherein

-   -   R₁ and R₂ are C₅-C₁₂alkyl;    -   R₃ is C₂-C₁₂alkenyl, especially allyl; and    -   R₄ is hydrogen; or C₁-C₅alkyl.

Preference is further given to compounds of formula (1) wherein

-   -   R₁ and R₂ are C₅-C₁₂alkyl;    -   R₃ is phenyl; or phenyl-C₁-C₄alkyl; especially benzyl; and    -   R₄ is hydrogen; or C₁-C₅alkyl.

Examples of compounds used in accordance with the invention correspondto formulae

Preparation of the compounds of formula (1) is carried out in a mannerknown per se by reacting the appropriate phenylmagnesium bromidecompound of formula (1c) in a Grignard reaction with cyanuric chloride(formula (1b)) to form the dichlorotriazine compound of formula (1d),introducing resorcinol groups by Friedel-C rafts acylation of resorcinol(formula (1e)) in the presence of a Lewis acid, especially aluminiumchloride, and etherifying the free hydroxyl groups in the p- ando-positions of the compound of formula (1f), according to the meaningsof the radicals R₁, R₂ and R₃, by alkylation to form the compound offormula (1), in accordance with the following scheme:

Details thereof can be found in the Preparation Examples.

The compounds of formula (1) are suitable as UV absorbers, especially aslight-protective agents for human skin and hair.

Component (b) of the composition according to the invention preferablycomprises a UV absorber of formula

wherein

-   -   L₁ is C₁-C₂₂alkyl, C₂-C₂₂alkenyl or C₅-C₇cycloalkyl;    -   L₂ and L₆ are each independently of the other hydrogen, hydroxy,        halogen, C₁-C22alkyl or halomethyl;    -   L₃, L₅ and L₇ are each independently of the others hydrogen,        hydroxy, OL₁, halogen, C₁-C₂₂alkyl or halomethyl;    -   L₄ is hydrogen, hydroxy, —OL,, halogen, C₁-C₂₂alkyl, phenyl or        halomethyl;    -   L₁₂ is C₁-C₂₂alkyl, phenyl-C₁-C₅alkyl, C₅-C₇cycloalkyl, OL₁ or,        preferably, a group of        and    -   j is 0, 1, 2 or 3.

C₂-C₂₂Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl,3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl,n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl orn-octadec-4-enyl.

C₅-C₇Cycloalkyl is cyclopentyl, cycloheptyl or, preferably, cyclohexyl.

Halogen is fluorine, bromine, iodine or, preferably, chlorine.

Very special preference is given, in accordance with the invention, tocompounds of formula (6) wherein

-   -   L₁ is C₁-C₂₂alkyl; C₂-C₂₂alkenyl; or C₅-C₇cycloalkyl;    -   L₂, L₃, L₅ and L₇ are hydrogen; and    -   L₄ and L₆ are as defined for formula (6).

Very special preference is given to hydroxyphenyltriazine compounds offormula

wherein

-   -   L₁ is C₁-C22alkyl, C₂-C₂₂alkenyl or C₅-C₇cycloalkyl; and    -   L₉ is C₁-C₅alkyl; or C₁-C₅alkoxy.

Very special preference is given to the use of the hydroxyphenyltriazinecompound of formula

as component (b₁) in the composition according to the invention.

Further hydroxyphenyltriazine compounds of component (b₁) the use ofwhich is preferred correspond to formula

wherein

-   -   L₁ is C₁-C₂₂alkyl; preferably C₁-C₅alkyl; and especially methyl.

Preference is also given to the use, as component (b₂), of benzotriazolecompounds of formula

-   -   R₅ is C₁-C₁₂alkyl; C₁-C₅alkoxy; C₁-C₅alkoxycarbonyl;        C₅-C₇cycloalkyl; C₆-C₁₀aryl; aralkyl;    -   —SO₃M; or a radical of formula (10a)    -   R₇ is hydrogen; C₁-C₅alkyl; C₁-C₅alkoxy; halogen, preferably        chlorine; or hydroxy;    -   R₈ and R₉ are each independently of the other hydrogen; or        C₁-C₅alkyl;    -   m is 1 or 2;    -   n is 0 or 1;    -   when m=1,    -   R₆ is hydrogen; unsubstituted or phenyl-substituted C₁-C₁₂alkyl;        or C₆-C₁₀aryl;    -   when m=2,    -   R₆ is a direct bond; or —(CH₂)_(p)—; and    -   p is from 1 to 3.

Preferred benzotriazole compounds of component (b) suitable for useaccording to the invention correspond to formula

R₅ is C₁-C₁₂alkyl, especially C₁-C₈alkyl; very especially the compoundof formula

There is furthermore used, as component (b₃), preferably1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione orbutylmethoxydibenzoylmethane or, as component (b₄), a camphorderivative.

By virtue of its lipophilicity, the UV absorber composition according tothe invention, on its own or together with other soluble organic UVabsorbers, can readily be incorporated, in accordance with knownmethods, into oil- and fat-containing cosmetic formulations such as, forexample, oils, O/W or W/O emulsions, fat-containing formulations instick form, or gels.

The compounds of the formula (1) according to the present invention areparticularly suitable as UV filters, i.e. for protectingultraviolet-sensitive organic materials, in particular the skin and hairof humans and animals, from the harmful effects of UV radiation. Thesecompounds are therefore suitable as sunscreens in cosmetic,pharmaceutical and veterinary medical preparations. These compounds canbe used both in dissolved form and in the micronized state.

The UV absorbers according to the present invention can be used eitherin the dissolved state (soluble organic filters, solubilized organicfilters) or in the micronised state (nanoscalar organic filters,particulate organic filters, UV-absorber pigments). Any known processsuitable for the preparation of microparticles can be used for thepreparation of the micronised UV absorbers, for example:

-   -   wet-milling (low viscous micronisation process for pump-able        dispersions), with a hard grinding medium, for example zirconium        silicate balls in a ball mill and a protective surfactant or a        protective polymer in water or in a suitable organic solvent;    -   wet-kneading (high viscositiy micronisation process for non        pump-able pastes) using a continuous or discontinuous (batch)        kneader. For a wet-kneading process a solvent (water or        cosmetically acceptable oils), a grinding-aid (surfactant,        emulsifier) and a polymeric grinding aid may be used.    -   spray-drying from a suitable solvent, for example aqueous        suspensions or suspensions containing organic solvents, or true        solutions in water, ethanol, dichloroethane, toluene or        N-methylpyrrolidone etc..    -   by the expansion according to the RESS process (Rapid Expansion        of Supercritical Solutions) of supercritical fluids (e.g. CO₂)        in which the UV filter or filters is/are dissolved, or the        expansion of fluid carbon dioxide together with a solution of        one or more UV filters in a suitable organic solvent;    -   by reprecipitation from suitable solvents, including        supercritical fluids (GASR process=Gas Anti-Solvent        Recrystallisation/PCA process=Precipitation with Compressed        Anti-solvents).

As milling apparatus for the preparation of the micronised organic UVabsorbers there may be used, for example, a jet mill, ball mill,vibratory mill or hammer mill, preferably a high-speed mixing mill. Evenmore preferably mills are modern ball mills, manufacturers of thesemill-types are for example Netzsch (LMZ-mill), Drais (DCP-viscoflow orcosmo), Bühler AG (centrifugal mills) or Bachhofer. The grinding ispreferably carried out with a grinding aid. As kneading apparatus forthe preparation of the micronised organic UV absorbers examples aretypical sigma-hook batch kneaders but also serial batch kneaders(IKA-Werke) or continuous kneaders (Continua from Werner undPfleiderer).

Useful low molecular weight grinding aids for all the above micronizingprocesses are surfactants and emulsifiers as disclosed below in thechapters “emulsifiers” and “surfactants”.

Useful polymeric grinding aids for water dispersion are cosmeticallyacceptable water soluble polymers for example: acrylates (Salcaretypes), modified or non-modified polysaccharides, polyglucosides orxanthan gum. Furthermore an alkylated vinylpyrrolidone polymer, avinyl-pyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkylpolyglucoside, ceteareth-25 or a phospholipid may be used. Oildispersions may contain cosmetically acceptable waxy polymers or naturalwaxes as polymeric grinding aid to adjust viscosity during and afterprocessing.

Useful solvents are water, brine, (poly-)ethylene glycol or glycerinefor water-soluble dispersions and also cosmetically acceptable oils suchas those described under “emollients” for oil-soluble dispersions.

The micronised UV absorbers so obtained usually have an average particlesize from 0.02 to 2 micrometers, preferably from 0.05 to 1.5 micrometersand more especially from 0.1 to 1.0 micrometers.

The UV absorbers can also be used dry in powder form. For that purposethe UV absorbers are subjected to known grinding methods, such as vacuumatomization, countercurrent spray-drying etc.. Such powders have aparticle size of from 0.1 micrometer to 2 micrometers. To avoid theoccurrence of agglomeration, the UV absorbers can be coated with asurface-active compound prior to the pulverisation process, for examplewith an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipidor a known polymer, such as PVP, an acrylate etc.

The cosmetic formulations or pharmaceutical compositions according tothe present invention can also contain one or more than one further UVfilter as described in table 1-3.

The cosmetic or pharmaceutical preparations can be prepared byphysically mixing the UV absorber(s) with the adjuvant using customarymethods, for example by simply stirring together the individualcomponents, especially by making use of the dissolution properties ofalready known cosmetic UV absorbers, for example octyl methoxycinnamate, salicylic acid isooctyl ester, etc. The UV absorber can beused, for example, without further treatment, or in the micronisedstate, or in the form of a powder.

Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight,based on the total weight of the composition, of one UV absorber or UVabsorber mixtures.

Preference is given to the use of mixing ratios of the UV absorber offormula (1) according to the invention and optionally furtherlight-protective agents (as described in table 1-3) from 1:99 to 99:1,especially from 1:95 to 95:1 and preferably from 10:90 to 90:10, basedon weight. Of special interest are mixing ratios of from 20:80 to 80:20,especially from 40:60 to 60:40 and preferably approximately 50:50. Suchmixtures can be used, inter alia, to improve solubility or increase UVabsorption.

The UV absorbers of formula (1) according to the present invention orcombinations of UV filters are useful for the protection of skin, hairand/or natural or artificial hair color. TABLE 1 Suitable UV filtersubstances which can be additionally used with the UV absorbersaccording to the present invention p-aminobenzoic acid derivatives, forexample 4-dimethylaminobenzoic acid 2-ethylhexyl ester; salicylic acidderivatives, for example salicylic acid 2-ethylhexyl ester; benzophenonederivatives, for example 2-hydroxy-4-methoxybenzophenone and its5-sulfonic acid derivative; dibenzoylmethane derivatives, for example1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)- propane-1,3-dione;diphenylacrylates, for example 2-ethylhexyl2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;3-imidazol-4-ylacrylic acid and esters; benzofuran derivatives,especially 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and EP-A-613 893; polymeric UVabsorbers, for example the benzylidene malonate derivatives described inEP-A-709 080; cinnamic acid derivatives, for example the4-methoxycinnamic acid 2-ethylhexyl ester and isoamyl ester or cinnamicacid derivatives described in US-A-5 601 811 and WO 97/00851; camphorderivatives, for example 3-(4′-methyl)benzylidene-bornan-2-one,3-benzylidene- bornan-2-one, N-[2(and4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate, 3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonicacid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts;camphorbenzalkonium methosulfate; hydroxyphenyltriazine compounds, forexample 2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;benzotriazole compounds, for example2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol; trianilino-s-triazine derivatives,for example 2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5- triazineand the UV absorbers disclosed in US-A-5 332 568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838; 2-phenylbenzimidazole-5-sulfonic acidand salts thereof; menthyl o-aminobenzoates; physical sunscreens coatedor not coated, such as titanium dioxide, zinc oxide, iron oxides, mica,MnO, Fe₂O₃, Ce₂O₃, Al₂O₃, ZrO₂. (surface coatings:polymethylmethacrylate, methicone (methylhydrogenpolysiloxane asdescribed in CAS 9004-73-3), dimethicone, isopropyl titaniumtriisostearate (as described in CAS 61417-49-0), metal soaps such asmagnesium stearate (as described in CAS 4086-70-8), perfluoroalcoholphosphate as C9-15 fluoroalcohol phosphate (as described in CAS74499-44-8; JP 5-86984, JP 4-330007)). The primary particle size is anaverage of 15 nm-35 nm and the particle size in dispersion is in therange of 100 nm-300 nm. aminohydroxy-benzophenone derivatives disclosedin DE 10011317, EP 1133980 and EP 1046391 phenyl-benzimidazolederivatives as disclosed in EP 1167358 the UV absorbers described in“Sunscreens”, Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker, Inc., NewYork and Basle or in Cosmetics & Toiletries (107), 50ff (1992) also canbe used as additional UV protective substances.

TABLE 2 Suitable UV filter substances which can be additionally usedwith the UV absorbers according to the present invention are describedin the following patents; (preferred are the compounds in the 2^(nd)column) DE 100331804 Tab 1 p 4, tab 2 + 3 p 5 EP 613893 Ex 1-5 + 15, T1, pp 6-8 EP 1000950 Comp. in table 1, pp 18-21 EP 1005855 T 3, p 13 EP1008586 Ex 1-3, pp 13-15 EP 1008593 Ex 1-8, pp 4-5 EP 1027883 CompoundVII, p 3 EP 1027883 Comp I-VI, p 3 EP 1028120 Ex 1-5, pp 5-13 EP 1059082Ex 1; T 1, pp 9-11 EP 1060734 T 1-3, pp 11-14 EP 1064922 Compounds 1-34,pp 6-14 EP 1081140 Ex 1-9, pp 11-16 EP 1103549 Compounds 1-76, pp 39-51EP 1108712 4,5-Dimorpholino-3-hydroxypyridazine EP 1123934 T 3, p 10 EP1129695 Ex 1-7, pp 13-14 EP 1167359 Ex 1 p11 and ex 2 p 12 EP 420707 B1Ex 3, p 13 (CAS Regno No. 80142-49-0) EP 503338 T 1, pp 9-10 EP 517103Ex 3, 4, 9, 10 pp 6-7 EP 517104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 EP626950 all compounds EP 669323 Ex 1-3, p 5 EP 780382 Ex 1-11, pp 5-7 EP823418 Ex 1-4, pp 7-8 EP 826361 T 1, pp 5-6 EP 832641 Ex 5 + 6 p 7; t 2,p 8 EP 832642 Ex 22, T 3 pp, 10-15; T 4, p 16 EP 852137 T 2, pp 41-46 EP858318 T 1, p 6 EP 863145 Ex 1-11, pp 12-18 EP 895776 Comp. in rows48-58, p 3; R 25 + 33, p 5 EP 911020 T 2, p 11-12 EP 916335 T 2-4, pp19-41 EP 924246 T 2, p 9 EP 933376 Ex 1-15, pp 10-21 EP 944624 Ex 1 + 2,pp 13-15 EP 945125 T 3 a + b, pp 14-15 EP 967200 Ex 2; T 3-5, pp 17-20EP 969004 Ex 5, T 1, pp 6-8 JP 2000319629 CAS Reg. No. 80142-49-0,137215-83-9, 307947-82-6 US 5635343 all compounds on pp 5-10 US 5338539Ex 1-9, pp 3 + 4 US 5346691 Ex 40, p 7; T 5, p 8 US 5801244 Ex 1-5, pp6-7 WO 0149686 Ex 1-5, pp 16-21 WO 0168047 Tables on pp 85-96 WO 0181297Ex 1-3 pp 9-11 WO 0238537 All compounds p 3, compounds on rows 1-10 p 4WO 9217461 Ex 1-22, pp 10-20 WO 9220690 Polymeric comp in examples 3-6WO 9301164 T 1 + 2, pp 13-22 WO 9714680 Ex 1-3, p 10(Abbreviations T: table, R: row, Comp: compound, Ex: compound(s) ofpatent example, p: page)

TABLE 3 Suitable UV filter substances which can be additionally usedwith the UV absorbers according to the present invention No. ChemicalName CAS No. 1(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo-  36861-47-9[2.2.1]heptan-2-one 21,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one 15087-24-8 3 (2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-4 4 2,4-dihydroxybenzophenone   131-56-6 52,2′,4,4′-tetrahydroxybenzophenone   131-55-5 6 2-Hydroxy-4-methoxybenzophenone;   131-57-7 7 2-Hydroxy-4-methoxy benzophenone-5-sulfonicacid  4065-45-6 8 2,2′-dihydroxy-4,4′-dimethoxybenzophenone   131-54-4 92,2′-Dihydroxy-4-methoxybenzophenone   131-53-3 10Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts 56039-58-8 111-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3- 70356-09-1 dione 12 Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3- 52793-97-2 oxobicyclo[2,2,1]hept-2-ylidene)methyl]anilinium sulphate;22 3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate   118-56-9 23 Isopentylp-methoxycinnamate  71617-10-2 27 Menthyl-o-aminobenzoate   134-09-8 28Menthyl salicylate   89-46-3 29 2-Ethylhexyl2-cyano,3,3-diphenylacrylate  6197-30-4 30 2-ethylhexyl4-(dimethylamino)benzoate  21245-02-3 31 2-ethylhexyl 4-methoxycinnamate 5466-77-3 32 2-ethylhexyl salicylate   118-60-5 33 Benzoic acid,4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-,  88122-99-0tris(2-ethylhexyl) ester; 2,4,6-Trianilino-(p-carbo-2′-ethylhexyl-1′-oxi)-1,3,5-triazine 34 4-aminobenzoic acid   150-13-0 35 Benzoic acid,4-amino-, ethyl ester, polymer with oxirane 113010-52-9 382-phenyl-1H-benzimidazole-5-sulphonic acid  27503-81-7 39 2-Propenamide,N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2- 147897-12-9ylidene)methyl]phenyl]methyl]-, homopolymer 40 Triethanolaminesalicylate  2174-16-5 413,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-  90457-82-2bicyclo[2.2.1]heptane-1-methanesulfonic acid] 42 Titanium dioxide 13463-67-7 44 Zinc oxide  1314-13-2 452,2′-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl-103597-45-1 butyl)-phenol] 462,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4- 187393-00-6methoxyphenyl)-(1,3,5)-triazine 47 1H-Benzimidazole-4,6-disulfonic acid,2,2′-(1,4-phenylene)bis-, 180898-37-7 disodium salt 48 Benzoic acid,4,4′-[[6-[[4-[[(1,1- 154702-15-5dimethylethyl)amino]carbonyl]phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)ester 49 Phenol,2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3- 155633-54-8tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]- 50alpha-(trimethylsilyl)-omega-(trimethyl-silyloxy)poly[oxy(dimethyl)-207574-74-1silylene]-co-[oxy(methyl)(2-{p-[2,2-bis(ethoxycarbonyl)vinyl]-phenoxy}-1methyleneethyl)silylene]-co-[oxy(methyl)(2-{p-[2,2-bis(ethoxycarbonyl)vinyl]phenoxy}prop-1-enyl)silylene] 51Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-, monosodium salt 52 Benzoic acid,2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl ester 302776-68-7 531-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]- 156679-41-3propyl]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) 541-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2- 177190-98-6propenyl)amino]-, chloride 55 1H-Benzimidazole-4,6-disulfonic acid,2,2′-(1,4-phenylene)bis- 170864-82-1 56 1,3,5-Triazine,2,4,6-tris(4-methoxyphenyl)-  7753-12-0 57 1,3,5-Triazine,2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]- 208114-14-1 58 1-Propanaminium,3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1- 340964-15-0dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-, methyl sulfate (salt) 59 2-Propenoic acid,3-(1H-imidazol-4-yl)-   104-98-3 60 Benzoic acid, 2-hydroxy-,[4-(1-methylethyl)phenyl]methyl ester  94134-93-7 61 1,2,3-Propanetriol,1-(4-aminobenzoate)   136-44-7 62 Benzeneacetic acid,3,4-dimethoxy-a-oxo-  4732-70-1 63 2-Propenoic acid,2-cyano-3,3-diphenyl-, ethyl ester  5232-99-5

Suitable UV filter substances which can be additionally used with the UVabsorbers according to the present invention are any UV-A and UV-Bfilter substances.

The cosmetic or pharmaceutical preparations may be, for example, creams,gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions,wax/fat compositions, stick preparations, powders or ointments. Inaddition to the above mentioned UV filters, the cosmetic orpharmaceutical preparations may contain further adjuvants as describedbelow.

A water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/Wemulsions or microemulsions) the preparations contain, for example, from0.1 to 30% by weight, preferably from 0.1 to 15% by weight andespecially from 0.5 to 10% by weight, based on the total weight of thecomposition, of one or more UV absorbers, from 1 to 60% by weight,especially from 5 to 50% by weight and preferably from 10 to 35% byweight, based on the total weight of the composition, of at least oneoil component, from 0 to 30% by weight, especially from 1 to 30% byweight and preferably from 4 to 20% by weight, based on the total weightof the composition, of at least one emulsifier, from 10 to 90% byweight, especially from 30 to 90% by weight, based on the total weightof the composition, of water, and from 0 to 88.9% by weight, especiallyfrom 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according tothe invention may also contain one or one more additional compounds asdescribed below.

Fatty Alcohols

Guerbet alcohols based on fatty alcohols having from 6 to 18, preferablyfrom 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol,cetearyl alcohol, oleyl alcohol, octyl-dodecanol, benzoate of C12-C15alcohols, acetylated lanolin alcohol, etc..

Esters of Fatty Acids

Esters of linear C₆-C₂₄ fatty acids with linear C₃-C₂₄ alcohols, estersof branched C₆-C₁₃carboxylic acids with linear C₆-C₂₄ fatty alcohols,esters of linear C₆-C₂₄ fatty acids with branched alcohols, especially2-ethylhexanol, esters of hydroxycarboxylic acids with linear orbranched C₆-C₂₂ fatty alcohols, especially dioctyl malates, esters oflinear and/or branched fatty acids with polyhydric alcohols (for examplepropylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols,for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capricacid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselinic acid, linoleic acid, linolenic acid, elaeostearicacid, arachidic acid, gadoleic acid, behenic acid and erucic acid andtechnical-grade mixtures thereof (obtained, for example, in the pressureremoval of natural fats and oils, in the reduction of aldehydes fromRoelen's oxosynthesis or in the dimerisation of unsaturated fatty acids)with alcohols, for example, isopropyl alcohol, caproic alcohol, caprylalcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol,isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol,stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol,petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearylalcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucylalcohol and brassidyl alcohol and technical-grade mixtures thereof(obtained, for example, in the high-pressure hydrogenation oftechnical-grade methyl esters based on fats and oils or aldehydes fromRoelen's oxosynthesis and as monomer fractions in the dimerisation ofunsaturated fatty alcohols).

Examples of such ester oils are isopropyl myristate, isopropylpalmitate, isopropyl stearate, isopropyl isostearate, isopropyl oleate,n-butyl stearate, n-hexyl laurate, n-decyl oleate, iso-octyl stearate,iso-nonyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate,2-hexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyloleate, oleyl erucate, erucyl oleate, erucyl erucate, cetearyloctanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetylbehenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyloleate, myristyl stearate, myristyl palmitate, myristyl lactate,propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearylmalate, octyl hydroxystearate, etc..

Other Adjuvants

diethylhexyl 2,6- naphthalate, di-n-butyl adipate,di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecylacetate, and also diol esters, such as ethylene glycol dioleate,ethylene glycol diisotridecanoate, propylene glycoldi(2-ethylhexanoate), propylene glycol diisostearate, propylene glycoldipelargonate, butanediol diisostearate and neopentyl glycoldicaprylate. Esters of C₆-C₂₄ fatty alcohols and/or Guerbet alcoholswith aromatic carboxylic acids, saturated and/or unsaturated, especiallybenzoic acid, esters of C₂-C₁₂dicarboxylic acids with linear or branchedalcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10carbon atoms and from 2 to 6 hydroxy groups.

Natural or Synthetic Triglyceridesincluding Glyceryl Esters andDerivatives

Di- or tri-glycerides, based on C₆-C₁₈ fatty acids, modified by reactionwith other alcohols (caprylic/capric triglyceride, wheat germglycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-nsuch as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. orcastor oil, hydrogenated vegetable oil, sweet almond oil, wheat germoil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil,corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybeanoil, mink oil, sunflower oil, safflower oil, macadamia nut oil, oliveoil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil,etc.

Waxes including esters of long-chain acids and alcohols as well ascompounds having wax-like properties, e.g., carnauba wax, beeswax (whiteor yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffinwax, microcrystalline wax, ceresin, cetearyl esters wax, syntheticbeeswax, etc.. Also, hydrophilic waxes as cetearyl alcohol or partialglycerides.

Pearlescent Waxes:

Alkylene glycol esters, especially ethylene glycol distearate; fattyacid alkanolamides, especially coco fatty acid diethanolamide; partialglycerides, especially stearic acid monoglyceride; esters of polyvalent,unsubstituted or hydroxy-substituted carboxylic acids with fattyalcohols having from 6 to 22 carbon atoms, especially long-chainedesters of tartaric acid; fatty substances, for example fatty alcohols,fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, whichin total have at least 24 carbon atoms, especially laurone and distearylether; fatty acids, such as stearic acid, hydroxystearic acid or behenicacid, ring-opening products of olefin epoxides having from 12 to 22carbon atoms with fatty alcohols having from 12 to 22 carbon atomsand/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxygroups, and mixtures thereof.

Hydrocarbon Oils:

Mineral oil (light or heavy), petrolatum (yellow or white),microcrystalline wax, paraffinic and isoparaffinic compounds,hydrogenated isoparaffinic molecules as polydecenes and polybutene,hydrogenated polyisobutene, squalane, isohexadecane, isododecane andothers from plant and animal kingdom.

Silicones or Siloxanes (Organosubstituted Polysiloxanes)

Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, andalso amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-,glycoside- and/or alkyl-modified silicone compounds, which at roomtemperature may be in either liquid or resinous form. Linearpolysiloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM),dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (DowCorning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Alsosuitable are simethicones, which are mixtures of dimethicones having anaverage chain length of from 200 to 300 dimethylsiloxane units withhydrogenated silicates. A detailed survey by Todd et al. of suitablevolatile silicones may in addition be found in Cosm. Toil. 91, 27(1976).

Fluorinated or Perfluorinated Oils

Perfluorohexane, dimethylcyclohexane, ethylcyclopentane,polyperfluoromethylisopropyl ether.

Emulsifiers

Any conventionally usable emulsifier can be used for the compositions.Emulsifier systems may comprise for example: carboxylic acids and theirsalts: alkaline soap of sodium, potassium and ammonium, metallic soap ofcalcium or magnesium, organic basis soap such as lauric, palmitic,stearic and oleic acid etc.. Alkyl phosphates or phosphoric acid esters,acid phosphate, diethanolamine phosphate, potassium cetyl phosphate.Ethoxylated carboxylic acids or polyethylene glycol esters, PEG-nacylates. Linear fatty alcohols having from 8 to 22 carbon atoms,branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 molpropylene oxide with fatty acids having from 12 to 22 carbon atoms andwith alkylphenols having from 8 to 15 carbon atoms in the alkyl group.Fatty alcohol polyglycol ethers such as laureth-n, ceteareth-n,steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate,PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C₁₂-C₂₂fatty acid mono- and di-esters of addition products of from 1 to 30 molof ethylene oxide with polyols. Fatty acid and polyglycerol ester suchas monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates,polyglyceryl-3-diisostearates, triglyceryl diisostearates,polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures ofcompounds from a plurality of those substance classes are also suitable.Fatty acid polyglycolesters such as monostearate diethylene glycol,fatty acid and polyethylene glycol esters, fatty acid and saccharoseesters such as sucro esters, glycerol and saccharose esters such assucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters ofsaturated and unsaturated fatty acids having from 6 to 22 carbon atomsand ethylene oxide addition products. Polysorbate-n series, sorbitanesters such as sesquiisostearate, sorbitan, PEG-(6)-isostearatesorbitan, PEG-(10)-sorbitan laurate, PEG-1 7-dioleate sorbitan. Glucosederivatives, C₈-C₂₂ alkyl-mono and oligo-glycosides and ethoxylatedanalogues with glucose being preferred as the sugar component. O/Wemulsifiers such as methyl gluceth-20 sesquistearate, sorbitanstearate/sucrose cocoate, methyl glucose sesquistearate, cetearylalcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucosedioleate/methyl glucose isostearate. Sulfates and sulfonatedderivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl laurylsulfonate, linear sulfonated paraffins, sulfonated tetraproplynesulfonate, sodium lauryl sulfates, ammonium and ethanolamine laurylsulfates, lauryl ether sulfates, sodium laureth sulfates,sulfosuccinates, acetyl isothionates, alkanolamide sulfates, taurines,methyl taurines, imidazole sulfates. Amine derivatives, amine salts,ethoxylated amines, oxide amine with chains containing an heterocyclesuch as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetylpyridinium chloride, cetyl pyridinium bromide, quaternary ammonium suchas cetyltrimethylbromide ammonium bromide (CTBA), stearylalkonium. Amidederivatives, alkanolamides such as acylamide DEA, ethoxylated amidessuch as PEG-n acylamide, oxydamide. Polysiloxane/polyalkyl/polyethercopolymers and derivatives, dimethicone, copolyols, siliconepolyethylene oxide copolymer, silicone glycol copolymer. Propoxylated orPOE-n ethers (Meroxapols), poloxamers orpoly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene).Zwitterionic surfactants that carry at least one quaternary ammoniumgroup and at least one carboxylate and/or sulfonate group in themolecule. Zwitterionic surfactants that are especially suitable arebetaines, such as N-alkyl-N,N-dimethylammonium glycinates,cocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates,cocoacylaminopropyl-dimethylammonium glycinate and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to18 carbon atoms in the alkyl or acyl group and alsococoacylaminoethyl-hydroxyethylcarboxymethylglycinate, N-alkylbetaine,N-alkylaminobetaines. Alkyl-imidazolines, alkylopeptides,lipoaminoacids, self-emulsifying bases and the compounds as described inK. F.DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7,p250-251.

Non ionic bases such as PEG-6 beeswax (and) PEG-6 stearate (and)polyglyceryl -2-iso-stearate [Apifac], glyceryl stearate ( and) PEG-100stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S],sorbitan oleate (and) polyglyceryl-3 ricinoleate.[Arlacel 1689],sorbitan stearate and sucrose cocoate [arlatone 21 21], glycerylstearate and laureth-23 [Cera-synth 945], cetearyl alcohol and ceteth-20[Cetomacrogol Wax], cetearyl alcohol and polysorbate 60 and PEG-1 50 andstearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearylpolyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20[Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil[Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodiumcetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 andsteareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 andsteareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75stearate [Gelot 64], propylene glycol ceteth-3 acetate .[Hetester PCS],propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol andceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG -6 stearate and PEG-32stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20[Tefose 2000), PEG-6 stearate and ceteth-20 and glyceryl stearate andsteareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [TeginacidH, C, X].

Anionic alkaline bases such as PEG-2 stearate SE, glyceryl stearate SE[Monelgine, Cutina KD], propylene glycol stearate [Tegin P]. Anionicacid bases such as cetearyl alcohol and sodium cetearyl sulfate [LanetteN, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate[Lanette W], trilaneth-4 phosphate and glycol stearate and PEG-2stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate(Teginacid Special]. Cationic acid bases such as cetearyl alcohol andcetrimonium bromide.

The emulsifiers may be used in an amount of, for example, from 1 to 30%by weight, especially from 4 to 20% by weight and preferably from 5 to10% by weight, based on the total weight of the composition.

When formulated in O/W emulsions, the preferred amount of suchemulsifier system could represent 5% to 20% of the oil phase.

Adjuvants and Additives

The cosmetic/pharmaceutical preparations, for example creams, gels,lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fatcompositions, stick preparations, powders or ointments, may in additioncontain, as further adjuvants and additives, mild surfactants,super-fatting agents, consistency regulators, thickeners, polymers,stabilisers, biogenic active ingredients, deodorising activeingredients, anti-dandruff agents, film formers, swelling agents,further UV light-protective factors, antioxidants, hydrotropic agents,preservatives, insect repellents, self-tanning agents, solubilisers,perfume oils, colourants, bacteria-inhibiting agents and the like.

Super-Fatting Agents

Substances suitable for use as super-fatting agents are, for example,lanolin and lecithin and also polyethoxylated or acrylated lanolin andlecithin derivatives, polyol fatty acid esters, monoglycerides and fattyacid alkanolamides, the latter simultaneously acting as foamstabilisers.

Surfactants

Examples of suitable mild surfactants, that is to say surfactantsespecially well tolerated by the skin, include fatty alcohol polyglycolether sulfates, monoglyceride sulfates, mono- and/or di-alkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates,ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines and/or protein fatty acid condensation products, thelatter preferably being based on wheat proteins.

Consistency Regulators/Thickeners and Rheology Modifiers

Silicon dioxide, magnesium silicates, aluminium silicates,polysaccharides or derivatives thereof for example hyaluronic acid,xanthan gum, guar-guar, agar-agar, alginates, carrageenan, gellan,pectins, or modified cellulose such as hydroxycellulose,hydroxypropyl-methylcellulose. In addition polyacrylates or homopolymersof reticulated acrylic acids and polyacrylamides, carbomer (carbopoltypes 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) or Salcare rangesuch as Salcare SC80(steareth-10 allyl ether/acrylates copolymer),Salcare SC81 (acrylates copolymer), Salcare SC91 and Salcare AST(sodiumacrylates copolymer/PPG-1 trideceth-6), Sepigel305(polyacrylamide/laureth-7), Simulgel NS and Simulgel EG(hydro-xyethyl acrylate/sodium acryloyldimethyl taurate copolymer),Stabilen 30 (acrylates/vinyl isodecanoate crosspolymer), Pemulen TR-1(acrylates/C10-30 alkyl acrylate crosspolymer), Luvigel EM (sodiumacrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylatecopolymer), etc.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives, for example a quaternised hydroxymethyl celluloseobtainable under the name Polymer JR 400 from Amerchol, cationicstarches, copolymers of diallylammonium salts and acrylamides,quaternised vinylpyrrolidone/vinyl imidazole polymers, for exampleLuviquat® (BASF), condensation products of polyglycols and amines,quaternised collagen polypeptides, for example lauryl-dimoniumhydroxypropyl hydrolyzed collagen (Lamequat® L/Grünau), quaternisedwheat polypeptides, polyethyleneimine, cationic silicone polymers, forexample amidomethicones, copolymers of adipic acid anddimethylaminohydroxypropyidiethylenetriamine (Carta-retin/Sandoz),copolymers of acrylic acid with dimethyidiallylammonium chloride(Merquat 550/Chemviron), polyaminopolyamides, as described, for example,in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof,cationic chitin derivatives, for example of quarternised chitosan,optionally distributed as microcrystals; condensation products ofdi-haloalkyls, for example dibromobutane, with bisdialkylamines, forexample bisdimethyl-amino-1,3-propane, cationic guar gum, for exampleJaguar C17, Jaguar C-16 from Celanese, quarternised ammonium saltpolymers, for example Mirapol A-1 5, Mirapol AD-1, Mira-pol AZ-1 fromMiranol. As anionic, zwitterionic, amphoteric and non-ionic polymersthere come into consideration, for example, vinyl acetate/crotonic acidcopolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinylacetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinkedpolyacrylic acids and polyacrylic acids crosslinked with polyols,acrylamidopropyl-trimethyl-ammonium chloride /acrylate copolymers, octylacrylamide/methyl methacrylate-tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,polyvinyl-pyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactamterpolymers and also optionally derivatised cellulose ethers andsilicones. Furthermore the polymers as described in EP 1093796 (pages3-8, paragraphs 17-68) may be used.

Biogenic Active Ingredients

Biogenic active ingredients are to be understood as meaning, forexample, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbicacid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol,panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essentialoils, plant extracts and vitamin complexes.

Deodorising Active Ingredients

As deodorising active ingredients there come into consideration, forexample, anti-perspirants, for example aluminium chlorohydrates (see J.Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® ofHoechst AG, Frankfurt (FRG), there is available commercially, forexample, an aluminium chlorohydrate corresponding to formulaAl₂(OH)₅Cl×2.5 H₂O, the use of which is especially preferred (see J.Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it isalso possible to use aluminium hydroxyacetates and acidicaluminium/zirconium salts. Esterase inhibitors may be added as furtherdeodorising active ingredients. Such inhibitors are preferably trialkylcitrates, such as trimethyl citrate, tripropyl citrate, triisopropylcitrate, tributyl citrate and especially triethyl citrate (Hydagen CAT,Henkel), which inhibit enzyme activity and hence reduce odour formation.Further substances that come into consideration as esterase inhibitorsare sterol sulfates or phosphates, for example lanosterol, cholesterol,campesterol, stigmasterol and sitosterol sulfate or phosphate,dicarboxylic acids and esters thereof, for example glutaric acid,glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid,adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid andmalonic acid diethyl ester and hydroxycarboxylic acids and estersthereof, for example citric acid, malic acid, tartaric acid or tartaricacid diethyl ester. Antibacterial active ingredients that influence thegerm flora and kill or inhibit the growth of sweat-decomposing bacteriacan likewise be present in the preparations (especially in stickpreparations). Examples include chitosan, phenoxyethanol andchlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol(Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also provedespecially effective.

Anti-Dandruff Agents and Film Formers

As anti-dandruff agents there may be used, for example, climbazole,octopirox and zinc pyrithione. Customary film formers include, forexample, chitosan, microcrystalline chitosan, quarternised chitosan,polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,polymers of quaternary cellulose derivatives containing a highproportion of acrylic acid, collagen, hyaluronic acid and salts thereofand similar compounds.

Antioxidants

In addition to the primary light-protective substances it is alsopossible to use secondary light-protective substances of the antioxidantkind that interrupt the photochemical reaction chain triggered when UVradiation penetrates the skin or hair. Typical examples of suchanti-oxidants are amino acids (e.g. glycine, histidine, tyrosine,tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) andderivatives thereof, peptides, such as D,L-carnosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotinoids,carotenes, lycopene and derivatives thereof, chlorogenic acid andderivatives thereof, lipoic acid and derivatives thereof (e.g.dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols(e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and theglycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl,palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) andalso salts thereof, dilauryl thiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters,ethers, peptides, lipids, nucleotides, nucleosides and salts) and alsosulfoximine compounds (e.g. buthionine sulfoximines, homo-cysteinesulfoximine, buthionine sulfones, penta-, hexa-, hepta-thioninesulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids,palmitic acid, phytic acid, lactoferrin), hydroxy acids (e.g. citricacid, lactic acid, malic acid), humic acid, bile acid, bile extracts,bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof,unsaturated fatty acids and derivatives thereof (e.g. linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate,ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate),vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferylbenzoate of benzoin resin, rutinic acid and derivatives thereof,glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid,trihydroxybutyrophenone, uric acid and derivatives thereof, mannose andderivatives thereof, superoxide dismutase,N-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyl]sulfanilic acid (andsalts thereof, for example the disodium salts), zinc and derivativesthereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof (e.g.selenium methionine), stilbene and derivatives thereof (e.g. stilbeneoxide, trans-stilbene oxide) and the derivatives suitable according tothe invention (salts, esters, ethers, sugars, nucleotides, nucleosides,peptides and lipids) of those mentioned active ingredients. HALS(=“Hindered Amine Light Stabilizers”) compounds may also be mentioned.The amount of antioxidants present is usually from 0.001 to 30% byweight, preferably from 0.01 to 3% by weight, based on the weight of theUV absorber of formula (1).

Hydrotropic Agents

To improve the flow behaviour it is also possible to employ hydrotropicagents, for example ethoxylated or non ethoxylated mono-alcohols, diolsor polyols with a low number of carbon atoms or their ethers (e.g.ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin,ethylene glycol, ethylene glycol monoethylether, ethylene glycolmonobutylether, propylene glycol monomethylether, propylene glycolmonoethylether, propylene glycol monobutyl-ether, diethylene glycolmonomethylether; diethylene glycol monoethylether, diethylene glycolmonobutylether and similar products). The polyols that come intoconsideration for that purpose have preferably from 2 to 15 carbon atomsand at least two hydroxy groups. The polyols may also contain furtherfunctional groups, especially amino groups, and/or may be modified withnitrogen. Typical examples are as follows: glycerol, alkylene glycols,for example ethylene glycol, diethylene glycol, propylene glycol,butylene glycol, hexylene glycol and also polyethylene glycols having anaverage molecular weight of from 100 to 1000 Dalton; technicaloligoglycerol mixtures having an intrinsic degree of condensation offrom 1.5 to 10, for example technical diglycerol mixtures having adiglycerol content of from 40 to 50% by weight; methylol compounds, suchas, especially, trimethylolethane, trimethylol-propane,trimethylolbutane, pentaerythritol and dipentaerythritol; loweralkyl-glucosides, especially those having from 1 to 8 carbon atoms inthe alkyl radical, for example methyl and butyl glucoside; sugaralcohols having from 5 to 12 carbon atoms, for example sorbitol ormannitol; sugars having from 5 to 12 carbon atoms, for example glucoseor saccharose; amino sugars, for example glucamine; dialcohol amines,such as diethanolamine or 2-amino-1,3-propanediol.

Preservatives and Bacteria-Inhibiting Agents

Suitable preservatives include, for example, methyl-,ethy-, propyl-,butyl- parabens, benzalconium chloride,2-bromo-2-nitro-propane-1,3-diol, dehydroacetic acid, diazolidinyl Urea,2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde solution,methyldibromoglutanitrile, phenoxyethanol, sodiumhydroxymethylglycinate, imidazolidinyl urea, triclosan and furthersubstance classes listed in the following reference: K. F. DePolo—Ashort textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5,p210-219.

Bacteria-Inhibiting Agents

Typical examples of bacteria-inhibiting agents are preservatives thathave a specific action against gram-positive bacteria, such as2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine(1,6-di(4-chlorophenyl-biguanido)hexane) or TCC(3,4,4′-trichlorocarbanilide). A large number of aromatic substances andethereal oils also have antimicrobial properties. Typical examples arethe active ingredients eugenol, menthol and thymol in clove oil, mintoil and thyme oil. A natural deodorising agent of interest is theterpene alcohol farnesol (3,7,11 -tri-methyl-2,6,10-dodecatrien-1-ol),which is present in lime blossom oil. Glycerol monolaurate has alsoproved to be a bacteriostatic agent. The amount of the additionalbacteria-inhibiting agents present is usually from 0.1 to 2% by weight,based on the solids content of the preparations.

Perfume Oils

There may be mentioned as perfume oils mixtures of natural and/orsynthetic aromatic substances. Natural aromatic substances are, forexample, extracts from blossom (lilies, lavender, roses, jasmine,neroli, ylang-ylang), from stems and leaves (geranium, patchouli,petitgrain), from fruit (aniseed, coriander, carraway, juniper), fromfruit peel (bergamot, lemons, oranges), from roots (mace, angelica,celery, cardamom, costus, iris, calmus), from wood (pine-wood,sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses(tarragon, lemon grass, sage, thyme), from needles and twigs (spruce,pine, Scots pine, mountain pine), from resins and balsams (galbanum,elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials alsocome into consideration, for example civet and castoreum. Typicalsynthetic aromatic substances are, for example, products of the ester,ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substancecompounds of the ester type are, for example, benzyl acetate,phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalylacetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyibenzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexylpropionate, styrallyl propionate and benzyl salicylate. The ethersinclude, for example, benzyl ethyl ether; the aldehydes include, forexample, the linear alkanals having from 8 to 18 hydrocarbon atoms,citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde,hydroxycitronellal, lilial and bourgeonal; the ketones include, forexample, the ionones, isomethylionone and methyl cedryl ketone; thealcohols include, for example, anethol, citronellol, eugenol,isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; andthe hydrocarbons include mainly the terpenes and balsams. It ispreferable, however, to use mixtures of various aromatic substances thattogether produce an attractive scent. Ethereal oils of relatively lowvolatility, which are chiefly used as aroma components, are alsosuitable as perfume oils, e.g. sage oil, camomile oil, clove oil,melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berryoil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandinoil. Preference is given to the use of bergamot oil, dihydromyrcenol,lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamaldehyde,geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambreneforte, ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil,orange oil, allyl amyl glycolate, cy-clovertal, lavandin oil, muscatelsage oil, damascone, bourbon geranium oil, cyclohexyl salicylate,vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma,phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat alone or in admixture with one another.

Colourants

There may be used as colourants the substances that are suitable andpermitted for cosmetic purposes, as compiled, for example, in thepublication “Kosmetische Färbemittel” of the Farbstoffkommission derDeutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages81 to 106. The colourants are usually used in concentrations of from0.001 to 0.1% by weight, based on the total mixture.

Other Adjuvants

It is furthermore possible for the cosmetic preparations to contain, asadjuvants, anti-foams, such as silicones, structurants, such as maleicacid, solubilisers, such as ethylene glycol, propylene glycol, glycerolor diethylene glycol, opacifiers, such as latex, styrene/PVP orstyrene/acrylamide copolymers, complexing agents, such as EDTA, NTA,alaninediacetic acid or phosphonic acids, propellants, such aspropane/butane mixtures, N₂O dimethyl ether, CO₂, N₂ or air, so-calledcoupler and developer components as oxidation dye precursors, reducingagents, such as thioglycolic acid and derivatives thereof, thiolacticacid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, oroxidising agents, such as hydrogen peroxide, potassium bromate or sodiumbromate.

Suitable insect repellents are, for example, N,N-diethyl-m-toluamide,1,2-pentanediol or insect repellent 3535; suitable self-tanning agentsare, for example, dihydroxyacetone and/or erythrulose or dihydroxyacetone and/or dihydroxy acetone precursors as described in WO 01/85124and/or erythrulose.

Polymeric Beads or Hollow Spheres as SPF Enhancers

The combination of the UV-absorbers and UV-absorber combinations, listedabove, with SPF enhancers, such as non-active ingredients likestyrene/acrylates copolymer, silica beads, spheroidal magnesiumsilicate, crosslinked polymethylmethacrylates (PMMA; Micopearl M305Seppic), can maximize better the UV protection of the sun products.Holosphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflectradiation and the effective path length of the photon is thereforeincreased.( EP0893119). Some beads, as mentioned previously, provide asoft feel during spreading. Moreover, the optical activity of suchbeads, e.g.Micropearl M305, cans modulate skin shine by eliminatingreflection phenomena and indirectly may scatter the UV light. Whenformulated in O/W emulsions, the preferred amount of such SPF enhancersshould represent 1% to 10% of the total amount of the emulsion.

Cosmetic or Pharmaceutical Preparations

Cosmetic or pharmaceutical formulations are contained in a wide varietyof cosmetic preparations. There come into consideration, for example,especially the following preparations:

-   -   skin-care preparations, e.g. skin-washing and cleansing        preparations in the form of tablet-form or liquid soaps,        soapless detergents or washing pastes,    -   bath preparations, e.g. liquid (foam baths, milks, shower        preparations) or solid bath preparations, e.g. bath cubes and        bath salts;    -   skin-care preparations, e.g. skin emulsions, multi-emulsions or        skin oils;    -   cosmetic personal care preparations, e.g. facial make-up in the        form of day creams or powder creams, face powder (loose or        pressed), rouge or cream make-up, eye-care preparations, e.g.        eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix        creams; lip-care preparations, e.g. lipsticks, lip gloss, lip        contour pencils, nail-care preparations, such as nail varnish,        nail varnish removers, nail hardeners or cuticle removers;    -   foot-care preparations, e.g. foot baths, foot powders, foot        creams or foot balsams, special deodorants and antiperspirants        or callus-removing preparations;    -   light-protective preparations, such as sun milks, lotions,        creams or oils, sunblocks or tropicals, pre-tanning preparations        or after-sun preparations;    -   skin-tanning preparations, e.g. self-tanning creams;    -   depigmenting preparations, e.g. preparations for bleaching the        skin or skin-lightening preparations;    -   insect-repellents, e.g. insect-repellent oils, lotions, sprays        or sticks;    -   deodorants, such as deodorant sprays, pump-action sprays,        deodorant gels, sticks or roll-ons;    -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;    -   preparations for cleansing and caring for blemished skin, e.g.        synthetic detergents (solid or liquid), peeling or scrub        preparations or peeling masks;    -   hair-removal preparations in chemical form (depilation), e.g.        hair-removing powders, liquid hair-removing preparations, cream-        or paste-form hair-removing preparations, hair-removing        preparations in gel form or aerosol foams;    -   shaving preparations, e.g. shaving soap, foaming shaving creams,        non-foaming shaving creams, foams and gels, preshave        preparations for dry shaving, aftershaves or aftershave lotions;    -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de        toilette, eau de parfum, parfum de toilette, perfume), perfume        oils or perfume creams;    -   cosmetic hair-treatment preparations, e.g. hair-washing        preparations in the form of shampoos and conditioners, hair-care        preparations, e.g. pretreatment preparations, hair tonics,        styling creams, styling gels, pomades, hair rinses, treatment        packs, intensive hair treatments, hair-structuring preparations,        e.g. hair-waving preparations for permanent waves (hot wave,        mild wave, cold wave), hair-straightening preparations, liquid        hair-setting preparations, hair foams, hairsprays, bleaching        preparations, e.g. hydrogen peroxide solutions, lightening        shampoos, bleaching creams, bleaching powders, bleaching pastes        or oils, temporary, semi-permanent or permanent hair colourants,        preparations containing self-oxidising dyes, or natural hair        colourants, such as henna or camomile.        Presentation Forms

The final formulations listed may exist in a wide variety ofpresentation forms, for example:

-   -   in the form of liquid preparations as a W/O, OW, O/W/O, W/O/W or        PIT emulsion and all kinds of microemulsions,    -   in the form of a gel,    -   in the form of an oil, a cream, milk or lotion,    -   in the form of a powder, a lacquer, a tablet or make-up,    -   in the form of a stick,    -   in the form of a spray (spray with propellent gas or pump-action        spray) or an aerosol,    -   in the form of a foam, or    -   in the form of a paste.

Of special importance as cosmetic preparations for the skin arelight-protective preparations, such as sun milks, lotions, creams, oils,sunblocks or tropicals, pretanning preparations or after-sunpreparations, also skin-tanning preparations, for example self-tanningcreams. Of particular interest are sun protection creams, sun protectionlotions, sun protection milk and sun protection preparations in the formof a spray.

Of special importance as cosmetic preparations for the hair are theabove-mentioned preparations for hair treatment, especially hair-washingpreparations in the form of shampoos, hair conditioners, hair-carepreparations, e.g. pretreatment preparations, hair tonics, stylingcreams, styling gels, pomades, hair rinses, treatment packs, intensivehair treatments, hair-straightening preparations, liquid hair-settingpreparations, hair foams and hairsprays. Of special interest arehair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5%by weight of a UV absorber according to the invention, 12.0% by weightof sodium laureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine,3.0% by weight of sodium chloride, and water ad 100%.

For example, especially the following hair-cosmetic formulations may beused:

-   -   a₁) spontaneously emulsifying stock formulation, consisting of        the UV absorber according to the invention, PEG-6-C₁₀oxoalcohol        and sorbitan sesquioleate, to which water and any desired        quaternary ammonium compound, for example 4% minkamidopropyl        di-methyl-2-hydroxyethylammonium chloride or Quaternium 80 is        added;    -   a₂) spontaneously emulsifying stock formulation consisting of        the UV absorber according to the invention, tributyl citrate and        PEG-20-sorbitan monooleate, to which water and any desired        quaternary ammonium compound, for example 4% minkamidopropyl        dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is        added;    -   b) quat-doped solutions of the UV absorber according to the        invention in butyl triglycol and tributyl citrate;    -   c) mixtures or solutions of the UV absorber according to the        invention with n-alkylpyrrolidone.

Other typical ingredients in such formulations are preservatives,bactericides and bacteriostatic agents, perfumes, dyes, pigments,thickening agents, moisturizing agents, humectants, fats, oils, waxes orother typical ingredients of cosmetic and personal care formulationssuch as alcohols, poly-alcohols, polymers, electrolytes, organicsolvents, silicon derivatives, emollients, emulsifiers or emulsifyingsurfactants, surfactants, dispersing agents, antioxidants,anti-irritants and anti-inflammatory agents etc.

Examples of Cosmetic and Pharmaceutical Preparations (X=PreferedCombinations) O/W systems: Ingredients 1 2 3 4 5 6 7 8 EmulsifiersPotassium Cetyl Phosphate 2%-5% X Cetearyl Alcohol/DicetylPhosphate/Ceteth-10 Phosphate X 2%-6% Sodium Stearyl Phthalamate 1%-2% XCetearyl Alcohol/Behentrimonium Methosulfate 1%-5% X Quaternium-32 1%-5%X Dimethicone copolyol/Caprylic/Capric Triglyceride X 1%-4%Steareth-2/Steareth-21 2%-5% X Polyglyceryl Methyl Glucose Distearate1%-4% X Lipophilic emollient/dispersant oil 15%-20% X X X X X X X XFatty Alcohols and/or Waxes 1%-5% X X X X X X X X Thickeners (waterswellable thickeners) 0.5%-1.5% X X X X X X X X Preservatives 0.5%-1% XX X X X X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X X X XAntioxidants 0.05%-0.2% X X X X X X X X Water deionized Qs 100% X X X XX X X X Perfume oils 0.1%-0.4% X X X X X X X X UV-absorber according tothe invention 1%-20% X X X X X X X X UV-absorber as described in table1-3 0%-30% X X X X X X X X

W/O systems Ingredients 1 2 3 4 5 Emulsifiers Polyglyceryl-2Dipolyhydroxystearate 2%-4% X PEG-30 Dipolyhydroxystearate 2%-4% XRapeseed Oil Sorbitol Esters 1%-5% X PEG-45/Dodecyl Glycol Copolymer1%-5% X Sorbitan Oleate/Polycerol-3 ricinoleate 1%-5% X Lipophilicemollient/dispersant oil 10%-20% X X X X Fatty Alcohols and/or Waxes10%-15% X X X X Electrolytes (NaCl, MgSO₄) 0.5%-1% X X X X Polyol phase(Propylene glycol, glycerin) 1%-8% X X X X Preservatives 0.3%-0.8% X X XX Perfume oils 0.1%-0.4% X X X X Chelating agents (such as EDTA) 0%-0.2%X X X X Antioxidants 0.05%-0.2% X X X X Water deionized Qs 100% X X X XUV-absorber according to the invention 1%-20%. X X X X UV-absorber asdescribed in table 1-3 0%-30%. X X X X

W/Silicone systems Ingredients 1 2 3 4 Emulsifiers DimethiconeCopolyol/Cyclomethicone 5%-10% X X Laurylmethicone Copolyol 5%-10% X XSilicone phase Cyclopentasiloxane 15%-25% X X Dimethicone 15%-25% X XSilicone elastomer Dimethicone/Vinyldimethicone X X X X Crosspolymer1%-10% Humectant/polyols (Propylene X X X X glycol, glycerin) 2%-8%Chelating agents (such as EDTA) 0%-0.2% X X X X Antioxidants 0.05%-0.2%X X X X Preservatives 0.3%-0.8% X X X X Perfume oils 0.1%-0.4% X X X XWater deionized Qs 100% X X X X UV-absorber according to the invention1%-20% X X X X UV-absorber as described in table 1-3 0%-30% X X X X

Ingredients 1 2 3 4 5 6 7 8 Hydrocarbon oils X X Silicone oils X XPreservatives 0.3%-0.8% X X X X X X X X Water deionized Qs 100% X X X XX X X X Non ionic multifunctional X X X X X X X X W/O emulsifier 2%-5%Waxes 1%-5% X X X X X X X X Oil phase 20%-30% X X X X X X X X Fatty acidesters Natural and synthetic Triglycerides Hydrocarbon oils Siliconeoils Primary emulsion O1/W 15% X X X X X X X X Electrolytes (NaCl,MgSO₄) X X X X X X X X 0.1%-0.5% Water deionized Qs 100% X X X X X X X XPerfume oils 0.1%-0.4% X X X X X X X X UV-absorber according X X X X X XX X to the invention 1%-20% UV-absorber as X X X X X X X X described intable 1-3 0%-30%

Microemulsions Ingredients 1 2 3 4 5 6 7 8 9 10 Surfactants PEG-8Caprylic/Capric Glycerides 10%-25% X X X X X PPG-5-ceteth-20 10%-25% X XX X X Co-surfactants Polyglyceryl-6 Isostearate 5%-15% X XPolyglyceryl-3 Diisostearate 5%-15% X X Polyglyceryl-6 Dioleate 5%-15% XX PPG-10 Cetyl Ether 5%-15% X X Ethoxydiglycol 5%-15% X X Oil phase10%-80% X X X X X X X X X X Isostearyl Benzoate Isostearyl IsostearatePEG-7 Glyceryl Cocoate Cyclomethicone Polyalcohols/Humectants 1%-10% X XX X X X X X X X Preservatives 0.3-0.8% X X X X X X X X X X Perfume oils0.1%-0.4% X X X X X X X X X X Water Deioniz. qs 100% X X X X X X X X X XUV-absorber according to the invention X X X X X X X X X X 1%-20%UV-absorber as described in table 1-3 X X X X X X X X X X 0%-30%

O/W Spray emulsions Ingredients 1 2 3 4 5 6 Emulsifiers Alkyl Phosphates0.1%-5% X X X Glucosidic derivatives 0.1%-5% X X X SolubilisantsEthoxylated Glyceryl ethers 0.1%-1% X X Polysorbates 0.1%-1% X XEthoxylated Oleyl ethers 0.1%-1% X X Film forming agents PVP/VA Coplymer1%-10% X X X PVM/MA Copolymer 1%-10% X X X Oil phase 5%-20% X X X X X XNatural oils(Meadowfoam, Jojoba, Macadamia...) Fatty acids estersMineral oils Silicone oils Alcohol 0%-50% X X X X X X Thickeners0.1%-0.5% X X X X X X Polyacrylates Aluminium/Magnesium Silicates GumsNeutralizing agents 0%-1% X X X X X X Polyalcohols/Humectants 1%-5% X XX X X X Chelating agents (such as EDTA) 0%-0.2% X X X X X X Antioxidants0.05%-0.2% X X X X X X Water Deioniz. qs 100% X X X X X X Perfume oils0.1%-0.5% X X X X X X Preservatives 0.4%-1% X X X X X X UV-absorberaccording to X X X X X X the invention 1%-20% UV-absorber as described XX X X X X in table 1-3 0%-30%

G - Aqueous Ingredients 1 2 3 4 5 6 7 8 9 10 11 12 Thickeners NaturalThickener 1%-5% X X X X Semi-symthetic Thickener 1%-5% X X X X SyntheticThickener 0.3%-1.3% X X X X Neutralizing Agents 0.5%-1.5% X X X X X X XX X X X X Polyols - Humectants 5%-50% X X X X X X X X X X X X Filmforming agent/Conditioner Polyquaternium series 1%-5% X X X X X X PVM/MACopolymer 1%-5% X X X X X X Preservatives 0.5%-1% X X X X X X X X X X XX Chelating Agents (as EDTA) X X X X X X X X X X X X <0.1% WaterDeioniz. qs 100% X X X X X X X X X X X X Perfume oils 0.05%-0.4% X X X XX X X X X X X X Solubilisants Ethoxylated Glyceryl ethers X X X 0.1%-5%Polysorbates 0.1%-5% X X X Ethoxylated Oleyl ethers X X X X X X 0.1%-5%UV-absorber according to the X X X X X X X X X X X X invention 1%-20%UV-absorber as described in table X X X X X X X X X X X X 1-3 0%-30%

Oleogels Ingredients 1 2 3 4 5 6 7 8 9 10 Thickeners HydrogenatedLecithin 1%-10% X X Silica Dimethyl Silylate 1%-10% X X Silica 1%-5% X XC₂₄₋₂₈ Alkyl Dimethicone 1%-5% X X Aluminium or Magnesium Stearate 1%-5%X X Polyols - Humectants 5%-70% X X X X X X X X X X Oil phase 20%-90%Dicaprylyl Ether X X X Phenyl Trimethicone X X HydrogenatedPolyisobutene X Isopropyl Isostearate X X Oleogel basis (Mineral oil andhydrogenated X X Butylene/Ethylene or Ethylene/Propylene StyreneCopolymer) Silicone wax 1%-10% X X X X X X X X X X Dimethiconol BehenateDimethiconol Stearate Perfume oils 0.1%-0.5% X X X X X X X X X XAntioxidants 0.05%-0.2% X X X X X X X X X X UV-absorber according to theinvention X X X X X X X X X X 1%-20% UV-absorber as described in table1-3 X X X X X X X X X X 0%-30%

Light/dry cosmetic oils Ingredients 1 2 3 4 Lipophilic base Hydrocarbonoils 30%-70% X X Fatty acid esters branched or not 10%-50% X X Lightfeel agent Silicones/Siloxanes 0%-10% X X Perfluorinated oils andPerfluoroethers 0%-10% X X Viscosifying agents 0%-10% X X X X WaxesEsters of long chain acids and alcohols 0%-2% X X X X Antioxidants0.1%-1% X X X X Solubilisants/dispersing agents 0%-5% X X X X Perfumeoils 0.1%-0.5% X X X X UV-absorber according to the invention 1%-20%. XX X X UV-absorber as described in table 1-3 0%-30% X X X X

Foaming/mousse products Ingredients SD Alcohol 40 0%-8% X Propellant8%-15% X Nonionic Emulsifier/Surfactant 0.5%-3% X Corrosion Inhibitor0%-1% X Perfume oils 0.1%-0.5% X Preservatives 0.1%-1% X Miscellaneous0%-1% X UV-absorber according to the invention 1%-20%. X UV-absorber asdescribed in table 1-3 0%-30% X

Stick products Ingredients Waxes 15%-30% X Natural and silicone oils20%-75% X Lanoline derivatives 5%->50% X Esters of lanolin x Acetylatedlanolin x Lanolin oil x Colorants and pigments 10%-15% X Antioxidants0.1%-0.8% X Perfume oils 0.1%-2% X Preservatives 0.1%-0.7% X UV-absorberaccording to the invention 1%-20% X UV-absorber as described in table1-3 0%-30% X

Liquid and compact Ingredients 1 2 Liquid foundation Powder phase10%-15% X Oil phase 30%-40%; 75% X (only for anhydrous form)Thickener/suspending agents 1%-5% X Film forming polymers 1%-2% XAntioxidants 0.1%-1% X Perfume oils 0.1%-0.5% X Preservatives 0.1%-0.8%X Water deionized Qs 100% X Compact powder Powder phase 15%-50% X Oilphase 15%-50% X Polyol phase 5%-15% X Antioxidants 0.1%-1% X Perfumeoils 0.1%-0.5% X Preservatives 0.1%-0.8% X For the two product formsUV-absorber according to the invention 1%-20% X X UV-absorber asdescribed in table 1-3 0%-30% X X

Conditioning Shampoos Ingredients 1 Primary surfactants (listedpreviously) 5%-10% X Secondary surfactants (listed previously) 5%-15% XFoam Stabilizers (listed previously) 0%-5% X Water deionized 40%-70% XActives 0-10% X Conditioners x Refatting agents x Moisturizing agents xThickeners/Rheology mofifiers 0%-3% X Humectants 0%-2% X PH adjustingagents 0%-1% X Preservatives 0.05%-1% X Perfume oils 0.1%-1% XAntioxidants 0.05%-0.20% X Chelating Agents (EDTA) 0%-0.2% X Opascifyingagents 0%-2% X UV-absorber according to the invention 1%-20% XUV-absorber as described in table 1-3 0%-30% X

The cosmetic preparation according to the invention is distinguished byexcellent protection of human skin against the damaging effect ofsunlight.

In the Examples that follow percentages refer to weight. In the case ofthe triazine derivatives the amounts used refer to the pure substance.

EXAMPLE 1

Preparation of2-((2,4-(2-ethyl-hexyloxy)-phenyl))-4-((2-hydroxy-4-(2-ethyl-hexyloxy)-phenyl))-6-(4-methoxyphenyl)-(l..3.5)-triazine

31.5 g of2,4-bis((4-(2-ethyl-hexyloxy)-2-hydroxy)-phenyl))-6-(4-methoxyphenyl)-(1,3,5)-triazineof formula

200 g of dimethylformamide and 13.5 9 of sodium methanolate solution(30%) are introduced into a reaction flask. The contents of the flaskare slowly heated, with stirring, to the boiling temperature ofdimethylformamide (155° C.), with methanol being removed from thereaction mass by a separator. The contents of the flask are then cooledto 80° C. and 14.7 g of 3-bromomethylheptane are added. The reactionmass is stirred at 80° C. for 14 hours. For complete alkylation, 5 g of3-bromomethylheptane are subsequently added and the reaction iscontinued at 80° C. for 6 hours. 1500 ml of water and 8 g of formic acidare added to the reaction mass and the organic phase is taken up inabout 300 ml of toluene. The toluene solution is concentrated byevaporation at 80° C. in vacuo (0.5 mbar) (residue 37.4 g). The purecompound (practically colourless crystals; m.p.=53-55° C.) can beobtained by crystallisation from 2-butanol.

This compound has outstanding solubility in

-   -   glyceryl-trioctanoate>30% and    -   di-C₁₂-C₁₃alkylmalates>25%.

Spectral Properties: λ_(max)   322 nm ε  50443 liters/(mol/cm) E [1%, 1cm] (in dioxane) 681.62

EXAMPLE 2

Analogously to Example 1, compound (101a) is alkylated using butylbromide (i 3.9 g). 34 g of the compound of formula

are obtained,Analytical Data:

-   -   Empirical: C=74.1%; H=8.7%; N=5.9%    -   (Theoretical: C=73.8%; H=8.4%; N=6.1%)

EXAMPLE 3

As described in Example 1, the compound of formula (101a) is alkylatedusing allyl bromide (12 g). 32 g of the compound of formula

are obtained.Analytical Data:

-   -   Empirical: C=73.8%; H=8.2%; N=5.9%    -   (Theoretical: C=73.7%: H=8.0%; N=6.3%)

EXAMPLE 4

On alkylation of the compound of formula (101a) with benzyl bromide(10.3 g) according to Preparation Example 1, 35.7 g of the compound offormula

are obtained.

Analysis of the crude product shows:

-   -   Empirical: C=75.8%; H=7.99%;N=5.7%    -   (Theoretical: C=75.3%; H=7.7%; N=5.8%)

EXAMPLE 5

20.2 g (0.05 mol) of 2,4-bis(2,4-dihydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine of formula

are introduced, together with 200 ml of Methylcellosolve (Merck®) and8.8 g (0.11 mol) of 50% sodium hydroxide solution, into a 500 mlsulfonation flask provided with a stirrer, dropping funnel, condenserand internal thermometer. Stirring is carried out at 80° C. for 30minutes and, at the same temperature, 23.2 g (0.12 mol) of3-bromomethylheptane, dissolved in 25 ml of Methylcellosolve, are slowlyadded dropwise. The alkylation can be monitored by means of thin-layerchromatography. After reacting for 8 hours at 112-114° C., the startingmaterial can no longer be detected. Concentration to dryness byevaporation is carried out, the residue is taken up in 100 ml oftoluene/hexane (7 vol./3 vol.) and filtration is carried out to removethe insoluble material. For the purpose of purification, chromatographyis carried out on silica gel (column: diameter=5 cm, length=60 cm). Thecompound of formula (101a) is obtained in the form of a viscous,light-yellow resin which crystallises out after a few weeks. Yield: 24.6g (78.4% of theory). Crystallisation can be accelerated by adding seedcrystals.

In addition to the bisalkylated compound of formula (101a), about 1.4 gof the trisalkylated compound of formula (101) are formed in thereaction. The latter compound can be separated off as a by-productduring column chromatography of the reaction mass.

EXAMPLES 6 TO 8

Analogously to Example 3, 90 parts of the compound of formula (101a) canbe used in combination with

-   -   10 parts of the compound of formula (102) (=Example 6),    -   10 parts of the compound of formula (103) (=Example 7), or    -   10 parts of the compound of formula (104) (=Example 8).

Application Examples

Examples of Use for Cosmetic Light Protection

The light protection factors were determined by the method of Diffey andRobson, J. Soc. Cosmet. Chem. 40. 127-133 (1989) using an SPF analyser(Optometrix, SPF 290).

For the determination of photostability, the filter substances aredissolved in ethanol (c=1.10⁻⁵-5.10⁻⁵ M) and irradiated in a quartzcell, with stirring, using a metal halide lamp (Macam) (I_(UVB)=0.4-8.0mW/cm). For conversion to the solar spectrum (CIE D65 standard daylight,standardised to I_(UVB)=0.127 mW/cm²), the integral over the products ofthe wave-length-resolved lamp intensity and the corresponding absorptionvalues of the UV absorber in question between 290 and 400 nm iscalculated and divided by the integral over the products of the D65light intensities and the corresponding absorption values of the UVabsorber in question in the range between 290 and 400 nm. That factor ismultiplied by the half-life value for degradation under irradiation withthe metal halide lamp in order to obtain the corresponding half-lifevalue under solar irradiation. The half-life value for photo-degradationunder lamp irradiation is determined by UV spectroscopic measurement ofthe extinction at the wavelength of maximum absorbance and subsequentexponential fit. Using the method described, there are accordinglyobtained the half-life values for photo-degradation in D65 light.

EXAMPLE 9

O/W Emulsion Comprising the Compounds of Formulae (101), (103) and (106)(A): UV absorber mixture consisting of   3 g 95% by weight of thecompound of formula (101a) and  5% by weight of the compound of formula(101) sesame oil   10 g glyceryl stearate   4 g stearic acid   1 g cetylalcohol  0.5 g polysorbate 20  0.2 g (B): propylene glycol   4 gpropylparaben 0.05 g methylparaben 0.15 g triethanolamine  0.1 gcarbomer 934  0.1 g water ad 100 mlPreparation of the Emulsion

Phase (A):

Firstly, the UV absorber mixture is dissolved in sesame oil. The othercomponents of (A) are added thereto and combined.

Phase (B):

Propylparaben and methylparaben are dissolved in propylene glycol. 60 mlof water are then added, heating to 70° C. is carried out and thencarbomer 934 is emulsified therein.

Emulsion:

(A) is slowly added to (B) with vigorous application of mechanicalenergy. The volume is adjusted to 100 ml by the addition of water.

The sun protection factors and photostability values determined aregiven in Table 2. TABLE 2 Sun protection Photostability**) Concentrationfactor*) [h] UV absorber mixture 3% 9.1 1500 consisting of 95% by weightof the compound of formula (101a) and 5% by weight of the compound offormula (101)*)according to Diffey and Robson**)as half-life value of photo-degradation in D65 light in ethanolicsolution

The sun protection factor can be varied by means of the UV absorberconcentration.

The results show that the active substance mixture has a highphotostability and that a good sun protection factor can be obtainedwhen even a low concentration is used.

EXAMPLE 10

Daily Care Cream, Type O/W % w/w INCI-Name (as supplied) Part A GlycerylStearate (and) Cetearyl Alcohol 4.0 (and) Cetyl Palmitate (and)Cocoglycerides Ceteareth-12 4.0 Cetearyl Alcohol 2.0 Dicaprylyl Ether4.5 Ethylhexyl Stearate 4.0 Hexyl Laurate 3.5 Ethylhexyl Triazone 1.0Benzylidene Malonate Polysiloxane 2.0 HDI/Trimethylol Hexyl-LactoneCrosspolymer 5.0 (and) Silica Stearyl Dimethicone 1.0 Dimethicone 2.0Cetyl Alcohol 0.8 Mixture of 80% of the compound of 2.0 formula (101)and 20% of the compound of formula (101a) Part B Water qs to 100 Water(and) Scleroglucan (and) 2.0 Phenoxyethanol Glycerin 2.0 Part CSteareth-10 Allyl Ether/Acrylates 0.45 Copolymer Phenoxyethanol (and)Methylparaben 0.7 (and) Ethylparaben (and) Butylparaben (and)Propylparaben (and) Isobutylparaben Part D Aqua (and) Tocopheryl Acetate(and) 4.0 Caprylic/Capric Triglyceride (and) Polysorbate 80 (and)Lecithin Part E Water (and) Sodium Hydroxide qs Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately to 80° C. Part A is poured intopart B under continuous stirring. Afterwards the mixture is homogenizedwith an Ultra Turrax at 11 000 rpm for 20 sec. The mixture is cooleddown to 60° C. and part C is added. Below 30° C. part D is added and pHvalue is adjusted with sodium hydroxide between 6.5 and 7.0. FinallyFragrance is added.

EXAMPLE 11

Sun Protection Cream, Type O/W % w/w INCI-Name (as supplied) Part APolyglyceryl-3 Methylglucose Distearate 2.0 Decyl Oleate 5.7 IsopropylPalmitate 5.8 Caprylic/Capric Triglyceride 6.5 Mixture of 80% of thecompound of formula 2.0 (101) and 20% of the compound of formula (101a)Ethylhexyl Methoxycinnamate 5.0 Cetyl Alcohol 0.7 Part B Glycerin 3.0Carbomer 0.3 Water qs to 100 Part C Phenoxyethanol (and) Methylparaben(and) 0.5 Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Part D Methylene Bis-Benzotriazolyl 8.0Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) PropyleneGlycol (and) Xanthan Gum Water 20.0 Part E Water (and) Sodium Hydroxideqs Fragrance qs

Manufacturing Instruction

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenized with an Ultra Turraxby 11 000 rpm for 15 sec. The mixture is cooled down to 60° C. and partC and part D are incorporated. The mixture is homogenized for a shorttime again (5 sec./11 000 rpm) and further cooled down with a moderatestirring. At room temperature pH is adjusted with sodium hydroxidesolution between 5.5 and 6.0. Finally Fragrance is added.

EXAMPLE 12

Daily Care UV Protection Lotion % w/w INCI-Name (as supplied) Part AOleth-3 Phosphate 0.6 Steareth-21 2.5 Steareth-2 1.0 Cetyl Alcohol 0.8Stearyl Alcohol 1.5 Tribehenin 0.8 Isohexadecane 8.0 Mixture of 90% ofthe compound of formula 5.0 (101) and 10% of the compound of formula(101a) Part B Water qs to 100 Glycerin 2.0 Methylene Bis-Benzotriazolyl3.0 Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and)Propylene Glycol (and) Xanthan Gum Disodium EDTA 0.1 Part C Water 20.0Diazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate PropyleneGlycol 4.0 Part D Sodium Acrylates Copolymer (and) 1.5 ParaffiniumLiquidum (and) PPG-1 Trideceth-6 Cyclopentasiloxane 4.5 PEG-12Dimethicone 2.0 Tocopheryl Acetate 0.45 Water (and) Citric Acid Qs PartE Fragrance Qs

Manufacturing Instruction

Heat part A and part B separately up to 75° C. Pour part A into part Bunder continuous stirring. Immediately after the emulsification,incorporate in the mixture SF 1202 and SF 1288 from part D. Afterwardshomogenize with an Ultra Turrax at 11000 rpm for 30 sec. Let cool downto 65° C. and incorporate SALCARE® SC91. Under 50° C., add part C. At35° C. or below incorporate Vitamin E Acetate and subsequently adjustthe pH with Citric Acid. At room temperature add part E.

EXAMPLE 13

Sun Protection Cream, Type O/W % w/w INCI-Name (as supplied) Part APolyglyceryl-3 Methylglucose Distearate 2.0 Decyl Oleate 5.7 IsopropylPalmitate 5.8 Caprylic/Capric Triglyceride 6.5 Mixture of compound offormula (101) (90%) 2.0 and Butyl-methoxydibenzoyl-methane (CAS#70356-09-1) (10%) Ethylhexyl Methoxycinnamate 5.0 Cetyl Alcohol 0.7 PartB Glycerin 3.0 Carbomer 0.3 Water qs to 100 Part C Phenoxyethanol (and)Methylparaben (and) 0.5 Ethylparaben (and) Butylparaben (and)Propylparaben (and) Isobutylparaben Part D Methylene Bis-Benzotriazolyl8.0 Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and)Propylene Glycol (and) Xanthan Gum Water 20.0 Part E Water (and) SodiumHydroxide Qs Fragrance Qs

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenized with an Ultra Turraxat 11 000 rpm for 15 sec. The mixture is cooled down to 60° C. and partC and part D are incorporated. The mixture is homogenized for a shorttime again (5 sec./11 000 rpm). After cooling further down with amoderate stirring the pH is adjusted with sodium hydroxide at roomtemperature. A solution between pH 5.50 and 6.00 is obtained. FinallyFragrance is added.

EXAMPLE 14

Sun Protection Cream, Type O/W % w/w INCI-Name (as supplied) Part APolyglyceryl-3 Methylglucose Distearate 2.0 Decyl Oleate 5.7 IsopropylPalmitate 5.8 Caprylic/Capric Triglyceride 6.5 Mixture of the compoundof formula (101) 2.0 (90%) and Uvinul A Plus CAS# 302776-68-7 (10%)Ethylhexyl Methoxycinnamate 5.0 Cetyl Alcohol 0.7 Part B Glycerin 3.0Carbomer 0.3 Water qs to 100 Part C Phenoxyethanol (and) Methylparaben(and) 0.5 Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Part D Methylene Bis-Benzotriazolyl 8.0Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) PropyleneGlycol (and) Xanthan Gum Water 20.0 Part E Water (and) Sodium HydroxideQs Fragrance Qs

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenized with an Ultra Turraxat 11 000 rpm for 15 sec. After cooling down to 60° C. part C and part Dare incorporated. The mixture is homogenized for a short time again (5sec./11 000 rpm). After cooling further down with a moderate stirring pHis adjusted at room temperature with sodium ydroxide solution between5.50 and 6.00. Finally fragrance is added.

EXAMPLE 15

Sun Protection Cream, Type O/W % w/w INCI-Name (as supplied) Part APolyglyceryl-3 Methylglucose Distearate 2.0 Decyl Oleate 5.7 IsopropylPalmitate 5.8 Caprylic/Capric Triglyceride 6.5 Mixture of compound offormula (101) (90%) 2.0 and Benzyliden Camphor, CAS# 36861-47-9 (10%)Ethylhexyl Methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerin 3.0Carbomer 0.3 Water qs to 100 Part C Phenoxyethanol (and) Methylparaben(and) 0.5 Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Part D Methylene Bis-Benzotriazolyl 8.0Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) PropyleneGlycol (and) Xanthan Gum Water 20.0 Part E Water (and) Sodium HydroxideQs Fragrance Qs

Manufacturing Instruction

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenized with an Ultra Turraxat 11 000 rpm for 15 sec. After cooling down to 60° C. part C and part Dare incorporated. The mixture is homogenized for a short time again (5sec./11 000 rpm). After cooling further down with a moderate stirring pHis adjusted at room temperature with sodium hydroxide A solution betweenpH 5.50 and 6.00 is obtained. Finally Fragrance is added.

1. A UV absorber composition comprising (a) from 1 to 99% by weight of ahydroxyphenyltriazine compound of formula

 wherein R₁, R₂ and R₃ are each independently of the others C₁-C₁₈alkyl;C₂-C₁₀alkenyl; or phenyl-C₁-C₄alkyl; R₄ is hydrogen; or C₁-C₅alkyl; and(b) from 99 to 1% by weight of a further UV absorber selected from thegroup of (b₁) hydroxyphenyltriazines that are different from component(a), (b₂) benzotriazoles, (b₃) dibenzoylmethane derivatives and (b₄)camphor derivatives:
 2. A UV absorber composition according to claim 1,which comprises from 5 to 95% of component (a) and from 95 to 5% ofcomponent (b).
 3. A UV absorber composition according to claim 1,wherein R₁, R₂ and R₃ are each independently of the others C₅-C₁₂alkyl.4. A UV absorber composition according to claim 1, wherein R₁, R₂ and R₃have the same meaning.
 5. A UV absorber composition according to claim1, wherein component (a) corresponds to formula


6. A UV absorber composition according to claim 1, wherein, in formula(1), R₁ and R₂ are C₅-C₁₂alkyl; R₃ is C₂-C₁₂alkenyl; and R₄ is hydrogen;or C₁-C₅alkyl.
 7. A UV absorber composition according to claim 1,wherein, in formula (1), R₁ and R₂ are C₅-C₁₂alkyl; R₃ is phenyl; orphenyl-C₁-C₄alkyl; and R₄ is hydrogen; or C₁-C₅alkyl.
 8. A UV absorbercomposition according to claim 1, wherein component (b₁) corresponds toa UV absorber of formula

wherein L₁ is C₁-C₂₂alkyl, C₂-C₂₂alkenyl or C₅-C₇cycloalkyl; L₂ and L₆are each independently of the other hydrogen, hydroxy, halogen,C₁-C₂₂alkyl or halomethyl; L₃, L₅ and L₇ are each independently of theothers hydrogen, hydroxy, OL₁, halogen, C₁-C₂₂alkyl or halomethyl; L₄ ishydrogen, hydroxy, —OL₁, halogen, C₁-C₂₂alkyl, phenyl or halomethyl; L₁₂is C₁-C₂₂alkyl, phenyl-C₁-C₅alkyl, C₅-C₇cycloalkyl, OL₁ or, a group offormula

 and j is 0, 1, 2 or
 3. 9. A UV absorber composition according claim 8,wherein L₁₂ is a radical of formula

 and L₂, L₃, L₄, L₅ and L₆ are as defined in claim
 8. 10. A UV absorbercomposition according to claim 8, wherein L₁ is C₁-C₂₂alkyl;C₂-C₂₂alkenyl; or C₅-C₇cycloalkyl; L₂, L₃, L₅ and L₇ are hydrogen; andL₄ and L₆ are as defined in claim
 8. 11. A UV absorber compositionaccording claim 8, wherein the hydroxyphenyltriazine compoundcorresponding to component (b₁) corresponds to formula

wherein L₁ is C₁-C₂₂alkyl, C₂-C₂₂alkenyl or C₅-C₇cycloalkyl; and L₉ isC₁-C₅alkyl; or C₁-C₅alkoxy.
 12. A UV absorber composition according toclaim 11, wherein L₁ is C₅-C₂₀alkyl.
 13. A UV absorber compositionaccording to claim 8, wherein the hydroxyphenyltriazine compoundcorresponding to component (b₁) corresponds to formula


14. A UV absorber composition according to claim 8, wherein thehydroxyphenyltriazine compound corresponding to component (b₁)corresponds to formula

wherein L₁ is C₁-C₂₂alkyl.
 15. A UV absorber composition according toclaim 14, wherein L₁ is methyl.
 16. A UV absorber composition accordingto claim 1, wherein component (b₂) is a benzotriazole compound offormula

wherein R₅ is C₁-C₁₂alkyl; C₁-C₅alkoxy; C₁-C₅alkoxycarbonyl;C₅-C₇cycloalkyl; C₆-C₁₀aryl; aralkyl; —SO₃M; or a radical of formula

R₇ is hydrogen; C₁-C₅alkyl; C₁-C₅alkoxy; halogen, preferably chlorine;or hydroxy; R₈ and R₉ are each independently of the other hydrogen; orC₁-C₅alkyl; M is hydrogen or a monovalent counterion; m is 1 or 2; n is0 or 1; when m=1, R₆ is hydrogen; unsubstituted or phenyl-substitutedC₁-C₁₂alkyl; or C₆-C₁₀aryl; when m=2, R₆ is a direct bond; or—(CH₂)_(p)—; and p is from 1 to
 3. 17. A UV absorber compositionaccording to claim 16, wherein component (b₂) is a benzotriazolecompound of formula

wherein R₅ is C₁-C₁₂alkyl.
 18. A UV absorber composition according toclaim 16, wherein component (b₂) is a benzotriazole compound of formula


19. A UV absorber composition according to claim 1, wherein component(b₃) is 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione orbutylmethoxydibenzoylmethane.
 20. A UV absorber composition according toclaim 1, wherein component (b₄) is a camphor derivative.
 21. Use of thecompound of formula (1) according to claim 1 as a UV absorber.
 22. Amethod according to claim 21, wherein the compound of formula (1) isused as a light-protective agent for human skin and hair.
 23. A cosmeticformulation according to claim 1 comprising a compound of formula (1).24. A cosmetic formulation comprising a UV absorber compositionaccording to claim
 1. 25. A cosmetic formulation according to claim 24,which comprises further substances that absorb UV radiation in the UVBrange.
 26. A process for the preparation of a compound of formula (1),which comprises reacting the phenylmagnesium bromide compound of formula(1c) in a Grignard reaction with cyanuric chloride (formula (1b)) toform the dichlorotriazine compound of formula (1d), introducingresorcinol groups by Friedel-Crafts acylation of resorcinol (formula(1e)) in the presence of a Lewis acid, and etherifying the free hydroxylgroups in the p- and o-positions of the compound of formula (1f),according to the meaning of the radicals R₁, R₂ and R₃, by alkylation toform the compound of formula (1), in accordance with the followingscheme: